Method for oxidative cleavage of compounds with unsaturated double bond

ABSTRACT

A method for oxidative cleavage of a compound with an unsaturated double bond is provided. The method includes the steps of:(A) providing a compound (I) with an unsaturated double bond, a trifluoromethyl-containing reagent, and a catalyst;wherein, the catalyst is represented by Formula (II):M(O)mL1yL2z  (II);wherein, M, L1, L2, m, y, z, R1, R2 and R3 are defined in the specification; and(B) mixing the compound with an unsaturated double bond and the trifluoromethyl-containing reagent to perform an oxidative cleavage of the compound with the unsaturated double bond by using the catalyst in air or under oxygen atmosphere condition to obtain a compound represented by Formula (III):

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefits of the Taiwan Patent ApplicationSerial Number 109100028, filed on Jan. 2, 2020, the subject matter ofwhich is incorporated herein by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present disclosure relates to a method of oxidative cleavage and,more particularly, to a method of oxidative cleavage for a compound withan unsaturated double bond under an aerobic condition to obtain acarbonyl compound.

2. Description of Related Art

Oxidative cleavage is one of the important reactions for a compound withan unsaturated double bond, such as olefins. Generally, olefins can besubjected to an oxidative cleavage reaction by (1) ozone; (2) highoxidation state metal oxides, such as potassium permanganate (KMnO₄), orosmium tetroxide (OsO₄); and (3) Pd/Cu catalysis.

However, due to the use of strong oxidants and peroxides for thereaction, the oxidative cleavage of olefins has the disadvantages ofhigh cost and strict operating conditions, and it has difficulty in massproduction. In addition, half of the oxidation products in the oxidativecleavage reaction is not the expected product in almost all cases, andit causes additional waste and environmental pollution.

Therefore, there is a strong and urgent demand to develop a method ofoxidative cleavage for a compound with an unsaturated double bond toovercome the disadvantages of common oxidative cleavage and increaseeconomic benefits.

SUMMARY OF THE INVENTION

In view of this, the present disclosure provides a method for oxidativecleavage of a compound with an unsaturated double bond. The method canbe performed by using air or oxygen as an oxidant source under mildconditions, thereby overcoming the drawbacks of high cost or strictoperating conditions with respect to conventional oxidative cleavagereactions. At the same time, the other half of the oxidation productsare introduced with trifluoromethyl group, which greatly improveseconomic value.

The present disclosure provides a method for oxidative cleavage of acompound with an unsaturated double bond, comprising the steps of: (A)providing a compound (I) with an unsaturated double bond, atrifluoromethyl-containing reagent, and a catalyst;

wherein, R₁ and R₂ are each independently H, C₁₋₂₀ alkyl, C₃₋₂₀cycloalkyl, C₆₋₁₈ aryl, or C₄₋₁₈ heteroaryl, or R₁ and R₂ are fused tobe C₆₋₁₈ aralkyl; R₃ is H, C₁₋₁₀ alkyl, C₃₋₁₀ cycloalkyl, C₆₋₁₀ aryl, orC₄₋₁₀ heteroaryl, with the proviso that R₁, R₂ and R₃ are not H at thesame time; wherein the catalyst is represented by Formula (II):

M(O)_(m)L¹ _(y)L² _(z)  (II)

wherein, M is a metal selected from the group consisting of IVB, VB,VIB, and actinides; L¹ and L² are each a ligand; m and y are integersgreater than or equal to 1; and z is an integer greater than or equal to0;

(B) mixing the compound with an unsaturated double bond and thetrifluoromethyl-containing reagent to perform an oxidative cleavage ofthe compound with the unsaturated double bond by using the catalyst inair or under oxygen atmosphere condition to obtain a compoundrepresented by Formula (III):

The compound (1) with an unsaturated double bond according to thepresent disclosure may be an olefin compound. In the compound (I) withan unsaturated double bond, R₁ and R₂ are each independently H, C₁₋₂₀alkyl, C₃₋₂₀ cycloalkyl, C₆₋₁₈ aryl, or C₄₋₁₈ heteroaryl, or R₁ and R₂are fused to be C₆₋₁₈ aralkyl; R₃ is H, C₁₋₁₀ alkyl, C₃₋₁₀ cycloalkyl,C₆₋₁₀ aryl, or C₄₋₁₀ heteroaryl. Preferably, R₁ and R₂ are eachindependently H, C₁₋₁₀ alkyl, C₃₋₁₀ cycloalkyl, C₆₋₁₄ aryl, or C₄₋₁₂heteroaryl, or R₁ and R₂ are fused to be C₆₋₁₂ aralkyl; R₃ is H, C₁₋₆alkyl, C₃₋₆ cycloalkyl, C₆₋₁₀ aryl, or C₄₋₁₀ heteroaryl. Morepreferably, R₁ and R₂ are each independently H, C₁₋₆ alkyl, C₃₋₆cycloalkyl, C₆₋₁₄ aryl, or C₄₋₁₀ heteroaryl, or R₁ and R₂ are fused tobe C₆₋₁₀ aralkyl; R₃ is H, C₁₋₆ alkyl, or C₃₋₆cycloalkyl.

In addition, in the compound (I) with an unsaturated double bond, R, R₂and R₃ are not H at the same time

In the present disclosure, the catalyst may be represented by Formula(II). In the catalyst represented by Formula (II), L¹ is a ligand andpreferably selected from the group consisting of OTf, OTs, NTf₂,halogen, RC(O)CH₂C(O)R, OAc, OC(O)R, OC(O)CF₃, OMe, OEt, O-iPr, andbutyl, wherein R is alkyl (preferably C₁₋₆ alkyl, more preferably C₁₋₃alkyl). Furthermore, L² is a ligand and preferably selected from thegroup consisting of Cl, H₂O, CH₃OH, EtOH, THF, CH₃CN,

and ligand containing C═N unit.

In the present disclosure, the “ligand containing C═N unit” may comprisepyridine, oxazole, oxazoline, or imidazole. However, the presentdisclosure is not limited thereto. Specific example comprises2,2′-bipyridyl, 3-chloropyridine, 2,6-dichloropyridine,3,5-dichloropyridine, 2,6-di-tert-butylpyridine, 1-methylimidazole,1,2-dimethylimidazole. However, the present disclosure is not limitedthereto.

In one embodiment of the present disclosure, the “ligand containing C═Nunit” may be represented by Formula (IV):

wherein, R₄ and R₅ are each independently halogen, nitro, C₁₋₁₀ alkyl,C₆₋₁₈ aryl, or C₄₋₁₈ heteroaryl. Preferably, R₄ and R₅ may be eachindependently Cl, Br, NO₂ or C₁₋₁₀ alkyl.

In another embodiment, the “ligand containing C═N unit” may berepresented by Formula (V):

wherein R₆ and R₇ are each independently H, C₁₋₅ alkyl or C₃₋₄cycloalkyl.

Further, in the catalyst represented by Formula (II), M may be a metalselected from the group consisting of IVB, VB, VIB, and actinides. Inone aspect, M is a group IVB transition element, m is 1 and y is 2;wherein M may be Ti, Zr, or Hf. In another aspect, M is a group VBtransition element, m is 1 and y is 2 or 3; wherein M may be V or Nb. Inanother aspect, M is a group VIB transition element, m is 1 and y is 4;wherein M may be Mo, W, or Cr. In another aspect, M is a group VIBtransition element, m is 2 and y is 2; wherein M is Mo, W, or Cr. In yetanother aspect, M is selected from the actinides, m is 2 and y is 2;wherein M is U.

In addition, in the catalyst of Formula (II), z may be an integergreater than or equal to 0. When z is 0, the specific example of thecatalyst of Formula (II) may be MoO₂Cl₂, V(O)Cl₃, V(O)O-iPr)₃, V(O)Cl₂,V(O)(OAc)₂, V(O)(O₂CCF₃)₂, Ti(O)(acac)₂, Zr(O)Cl₂, Hf(O)Cl₂, Nb(O)Cl₂,MoO₂(acac)₂, V(O)(OTs)₂, VO(OTf)₂, or V(O)(NTf₂)₂. However, the presentdisclosure is not limited thereto. When z is an integer greater than 0,the specific example of the catalyst of Formula (II) may be any offormulas (II-1) to (II-4):

However, the present disclosure is not limited thereto.

The trifluoromethyl-containing reagent according to the presentdisclosure may be a monotrifluoromethyl- or perfluoroalkyl-containingreagent. The specific example comprises3,3-Dimethyl-1-(trifluoromethyl)-1,2-benziodoxole,3,3-Dimethyl-1-(perfluroalkyl)-1,2-benziodoxole,3-oxo-1-(trifluoromethyl)-1,2-benziodoxole,3-oxo-1-(perfluroalkyl)-1,2-benziodoxole, trifluomethyldibenzothiophenium salts, perfluoroalkyl dibenzothiophenium salt,CF₃SO₂Na, and CF₃(CF₂), SO₂Na (n=1-6). However, the present disclosureis not limited thereto.

In the compound represented by Formula (III), R₁ and R₂ are eachindependently H, C₁₋₂₀ alkyl, C₃₋₂₀ cycloalkyl, C₆₋₁₈ aryl, or C₄₋₁₈heteroaryl, or R₁ and R₂ fused to be C₆₋₁₈ aralkyl group. Preferably, R₁and R₂ are each independently H, C₁₋₁₀ alkyl, C₃₋₁₀ cycloalkyl, C₆₋₁₄aryl, or C₄₋₁₂ heteroaryl, or R₁ and R₂ fuse to be C₆₋₁₂ aralkyl group.More preferably, R₁ and R₂ are each independently H, C₁₋₆ alkyl, C₃₋₆cycloalkyl, C₆₋₁₂ aryl, or C₄₋₁₀ heteroaryl, or R₁ and R₂ fused to beC₆₋₁₀ aralkyl group. In one embodiment of the present disclosure, R₁ andR₂ are not H at the same time.

In the present disclosure, step (B) may further obtain atrifluoroketone- or trifluoroaldehyde-containing compound,trifluoroalkyl alcohol or a combination thereof.

wherein R₃ is H, C₁₋₁₀ alkyl, C₃₋₁₀ cycloalkyl, C₆₋₁₀ aryl, or C₄₋₁₀heteroaryl; n is an integer of 0 or 1 to 6.

In one embodiment of the present disclosure, R₃ is preferably H, C₁₋₆alkyl, C₃₋₆ cycloalkyl, C₆₋₁₀ aryl, or C₄₋₁₀ heteroaryl; n is an integerof 0 or 1 to 3. More preferably, R₃ is preferably H, C₁₋₆ alkyl, or C₃₋₆cycloalkyl; n is 0 or 1.

In another aspect of the present disclosure, the step (B) may furthercomprise adding an additive to the mixture of the compound with anunsaturated double bond and the trifluoromethyl-containing reagent,wherein the additive may be trimethylsilyl cyanide (TMSCN), anhydride ora combination thereof. However, the present disclosure is not limitedthereto.

Herein, the term “alkyl” of the present disclosure includesunsubstituted alkyl or alkyl group substituted with halogen, nitro,alkenyl, cycloalkyl, alkoxy, aryl, or heteroaryl. The terms“cycloalkyl”, “aryl”, “heteroaryl” and “aralkyl” include unsubstitutedgroups or groups substituted with alkyl, halogen, nitro, alkenyl,cycloalkyl, alkoxy, aryl, or heteroaryl.

In summary, the present disclosure introduces atrifluoromethyl-containing reagent into an oxidative cleavage reaction.The reaction can use air or oxygen as an oxidant source under mildconditions, and the reaction is conducted using a proper catalyst toobtain a corresponding ketone or aldehyde. In addition, because of theintroduction of the trifluoromethyl reagent, the other half of theoxidative cleavage reaction will be converted into trifluoromethyl orperfluoromethylketone, or trifluoromethyl aldehyde, perfluoroalkylaldehyde, and trifluoromethyl or perfluroalkyl ethanol, which can befurther used.

Other objects, advantages, and novel features of the invention willbecome more apparent from the following detailed description when takenin conjunction with the accompanying drawings.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Different embodiments of the present invention are provided in thefollowing description. These embodiments are meant to explain thetechnical content of the present invention, but not meant to limit thescope of the present invention. A feature described in an embodiment maybe applied to other embodiments by suitable modification, substitution,combination, or separation.

Preparation of an Unsaturated Double Bond with an Unsaturated DoubleBond

In a flame-dried, 50-mL, two-necked, round-bottomed flask was placedmethyltriphenylphosphonium bromide (3.0 equiv) dissolved in 1 mL THF(0.2 M) at 0° C. Then added tert-BuOK (3.0 equiv) stirred at 0° C. After30 minutes, add ketone or aldehyde (1.0 equiv) and let it warm to roomtemperature. After having been complete of the reaction, the reactionwas quenched with H₂O and extracted with EtOAc for three times. Thecombined organic layers dried over MgSO₄, and the filtrate wasconcentrated. The crude product was purified using flash columnchromatography on silica gel with pure hexane as eluent to affordstyrene derivatives.

1-nitro-4-(prop-1-en-2-yl)benzene

¹H NMR (CDCl₃, 400 MHz) δ 8.19 (d, J=9.0 Hz, 2H), 7.60 (d, J=9.1 Hz,2H), 5.52 (t, J=0.8 Hz, 1H), 5.29 (t, J=1.3 Hz, 1H), 2.19 (dd, J=1.5,0.8 Hz, 3H); ¹³C NMR (CDCl₃, 100 MHz) δ 147.6, 147.0, 141.6, 126.2,123.6, 116.4, 21.6; TLC R_(f) 0.47 (hexane); HRMS (FI) Calcd forC₉H₉NO₂: 163.0628, found: 163.0628.

4-(prop-1-en-2-yl)phenyl acetate

¹H NMR (CDCl₃, 500 MHz) δ 7.47 (d, J=9.0 Hz, 2H), 7.05 (d, J=8.5 Hz,2H), 5.34 (s, 1H), 5.08 (s, 1H), 2.30 (s, 3H), 2.14 (s, 3H); ¹³C NMR(CDCl₃, 100 MHz) δ169.5, 150.0, 142.4, 140.0, 126.5, 121.2, 112.6, 21.8,21.1; TLC R_(f) 0.38 (hexane); HRMS (FI) Calcd for C₁₁H₁₂O₂: 176.0832,found: 176.0828.

1-methoxy-4-(prop-1-en-2-yl)benzene

¹H NMR (CDCl₃, 400 MHz) δ7.43 (d, J=8.9 Hz, 2H), 6.87 (d, J=8.9 Hz, 2H),5.29 (dq, J=1.6, 0.7 Hz, 1H), 4.99 (quin, J=1.5 Hz, 1H), 2.13 (t, J=0.9Hz, 3H), 3.82 (s, 3H); ¹³C NMR (CDCl₃, 100 MHz) δ 159.0, 142.5, 133.7,126.6, 113.5, 110.6, 55.3, 21.9; TLC R_(f) 0.42 (hexane); HRMS (FI)Calcd for C₁₀H₁₂O: 148.0883, found: 148.0887.

2-(prop-1-en-2-yl)naphthalene

¹H NMR (400 MHz, CDCl₃) δ 7.87-7.82 (m, 4H), 7.71-7.68 (m, 1H),7.51-7.44 (m, 2H), 5.56 (s, 1H), 5.22-5.21 (m, 1H), 2.29 (s, 3H); ¹³CNMR (100 MHz, CDCl₃) δ143.0, 138.3, 133.3, 132.8, 128.2, 127.7, 127.5,126.1, 125.8, 124.2, 123.9, 113.0, 21.8; TLC R_(f) 0.49 (hexane); HRMS(FI) Calcd for C₃H₁₀: 168.0934, found: 168.0928.

4-(prop-1-en-2-yl)pyridine

¹H NMR (CDCl₃, 400 MHz) δ 8.55 (d, J=6 Hz, 2H), 7.33 (d, J=5.2 Hz, 2H),5.57 (d, J=0.6 Hz, 1H), 5.26 (d, J 1.0 Hz, 2H), 2.14 (s, 3H); ¹³C NMR(CDCl₃, 100 MHz) δ 150.7, 149.4, 148.2, 140.7, 121.0, 119.9, 115.8,20.6; TLC R_(f) 0.30 (EtOAc/Hexane=1/5); HRMS (FI) Calcd for C₈H₉N:119.0730, found: 119.0730.

2-(prop-1-en-2-yl)pyridine

¹H NMR (CDCl₃, 400 MHz) 8.68 (td, J=4, 0.8 Hz, 1H), 8.03 (dd, J=8.0, 0.8Hz, 1H), 7.82 (dt, J=7.8, 1.6 Hz, 1H), 7.44-7.48 (m, 1H), 2.72 (s, 3H);¹³C NMR (CDCl₃, 100 MHz) δ 199.4, 153.1, 148.6, 136.4, 136.1, 126.7,121.1, 25.3; TLC R_(f)0.25 (EtOAc/Hexane=1/5); HRMS (FI) Calcd forC₈H₉N: 119.0730, found: 119.0729.

2-(prop-1-en-2-yl)thiophene

¹H NMR (400 MHz, CDCl₃) δ7.15 (dd, J=5.1, 1.1 Hz, 1H), 7.02 (dd, J=3.6,1.1 Hz, 1H), 6.96 (dd, J=5.1, 3.6 Hz, 1H), 5.37 (s, 1H), 4.94 (m, 1H),2.14 (m, 3H); ¹³C NMR (125 MHz, CDCl₃) δ145.8, 137.1, 127.2, 124.2,123.5, 111.1, 21.8; TLC R_(f) 0.43 (hexane); HRMS (FI) Calcd for C₇H₈S:124.0341, found: 124.0340.

Prop-1-en-2-ylcyclohexane

¹H NMR (CDCl₃, 400 MHz) δ 4.66 (s, 2H), 1.90-1.82 (m, 2H), 1.78-1.1.71(m, 7H), 1.30-1.11 (m, 6H); ¹³C NMR (CDCl₃, 100 MHz) δ 151.3, 107.8,45.5, 32.0, 26.8, 26.4, 20.9; TLC R_(f)0.6 (hexane); HRMS (FI) Calcd forC₉H₁₆: 124.1247, found: 124.1243.

3-bromoprop-1-en-2-yl)benzene

¹H NMR (CDCl₃, 400 MHz) δ 7.51-7.34 (m, 5H), 5.57 (s, 1H), 5.50 (s, 1H),4.40 (s, 2H); ¹³C NMR (CDCl₃, 100 MHz) δ 144.2, 137.6, 128.5, 128.3,126.1, 117.2, 34.2; TLC R_(f) 0.51 (hexane); HRMS (EI) Calcd for C₉H₉Br:195.9882, found: 195.9882.

(1-cyclopropylvinyl)benzene

¹H NMR (CDCl₃, 400 MHz) δ 7.62-7.59 (m, 2H), 7.37-7.26 (m, 3H), 5.28 (s,1H), 4.94 (s, 1H), 1.68-1.64 (m, 1H), 0.87-0.82 (m, 2H), 0.61-0.58 (m,2H); ¹³C NMR (CDCl₃, 100 MHz) δ149.4, 141.6, 128.1, 127.4, 126.1, 109.0,15.6, 6.7; TLC R_(f) 0.48 (hexane); HRMS (F) Calcd for C₁₁H₁₂: 144.0934,found: 144.0936.

(1-cyclohexylvinyl)benzene

¹H NMR (CDCl₃, 400 MHz) δ 7.36-7.25 (m, 5H), 5.14 (s, 1H), 5.01 (s, 1H),2.43 (t, J=11.6 Hz, 1H), 1.86-1.70 (m, 5H), 1.38-1.13 (m, 5H); ¹³C NMR(CDCl₃, 100 MHz) δ 154.99, 142.97, 128.10, 126.97, 126.62, 110.31,42.58, 32.71, 26.84, 26.45; TLC R_(f) 0.5 (hexane); HRMS (FI) Calcd forC₁₄H₁₈: 186.1403, found: 186.1402.

(3,3-dimethylbut-1-en-2-yl)benzene

¹H NMR (CDCl₃, 400 MHz) δ 7.31-7.26 (m, 3H), 7.16-7.14 (m, 2H), 5.18 (d,J=2.0 Hz, 1H), 4.77 (d, J=1.6 Hz, 1H), 1.13 (s, 9H); ¹³C NMR (CDCl₃, 100MHz) δ 159.8, 143.5, 129.0, 127.2, 126.2, 111.5, 36.1, 29.6; TLC R_(f)0.4 (hexane); HRMS (FI) Calcd for C₁₂H₁₆: 160.1247, found: 160.1247.

1-methylene-2,3-dihydro-1H-indene

¹H NMR (CDCl₃, 400 MHz) δ7.52-7.50 (m, 1H), 7.28-7.20 (m, 3H), 5.46 (t,J=2.4 Hz, 1H), 5.04 (t, J=2.4 Hz, 1H), 3.01-2.98 (m, 2H), 2.83-2.78 (m,2H); ¹³C NMR (CDCl₃, 125 MHz) δ150.6, 146.7, 141.1, 128.2, 126.4, 125.3,120.6, 102.4, 31.2, 30.1; TLC R_(f) 0.5 (hexane); HRMS (FI) Calcd forC₁₀H₁₀: 130.0777, found: 130.0776.

Synthesis of Catalyst (II)-1

In the present embodiment, the catalyst can be synthesized according tothe following chemical equation.

V(O)SO_(4(aq))+BaX_(2(aq))→V(O)X_(2(aq))+BaSO_(4(s))

V(O)SO_(4(aq))+Ba(OC(O)R)_(2(aq))→V(O)(OC(O)R)_(2(aq))+BaSO_(4(s))

V(O)SO_(4(aq))+Ba(OTf)_(2(aq))→V(O)(OTf)_(2(aq))+BaSO_(4(s))

V(O)SO_(4(aq))+Ba(OTs)_(2(aq))→V(O)(OTs)_(2(aq))+BaSO_(4(s))

V(O)SO_(4(aq))+Ba[(O₃SC₆H₄CHCH₂)_(n)]_(2(aq))→V(O)[(O₃SC₆H₄CHCH₂)_(n)]_(2(aq))+BaSO_(4(s))

In a flame-dried, 50-mL, two-necked, round-bottomed flask was placedvanadyl sulfate-VOSO₄-5H₂O (VOSO₄.5H₂O, 2.5 mmol) followed by additionof anhydrous MeOH (2.5 mL). To the above solution, a solution ofBa(OTf)₂ (1 equiv, 2.5 mmol) in MeOH (2.5 mL) was slowly added atambient temperature. After stirring for 30 minutes, the reaction mixturebecame turbid with copious amount of barium sulfate precipitation.Centrifugation (6000 rpm) for the mixture was performed for 30 minutes.The decanted solution was evaporated to give a dark green or faint bluesolid which was further dried at 120° C. for 4 hours in vacuo. Theresultant catalyst can be stored at ambient temperature for severalweeks in dry cabinet and can be used directly.

Synthesis of catalyst (II)-2

To the solution of 3,5-di-tert-butyl-2-hydroxybenzaldehyde (1217 mg, 5.0mmol, 1.0 equiv) in MeOH (12.5 mL) was added L-tert-leucine (721 mg, 5.5mmol, 1.1 equiv) or other 18 natural L-α-amino acids (721 mg, 5.5 mmol,1.1 equiv) and NaOAc (902 mg, 11.0 mmol, 2.2 equiv). After stirring at80° C. for 18 hours, the reaction mixture was gradually cooled toambient temperature and a solution of VOSO₄.5H₂O (1392 mg, 5.5 mmol, 1.1equiv) in MeOH (5.0 mL) was added. After the reaction was performed atambient temperature for 6 hours, the reaction mixture was concentratedunder reduced pressure. The resulting dark black solid was washed withwater (5×30 mL) and dried in vacuo to afford a pure oxidovanadium(IV)catalyst. The corresponding analytically pure oxidovanadium(V) methoxide(or hydroxide) complex (11-1) was obtained by re-crystallization fromoxygen saturated MeOH.

Catalyst (II-1)

Yield: 84%; black solid. ¹H NMR (CD₃OD, 500 MHz) S 8.60 (bs, 1H), 7.68(d, J=2.2 Hz, 1H), 7.48 (d, J=2.3 Hz, 1H), 4.14 (s, 1H), 1.47 (s, 9H),1.35 (s, 9H), 1.21 (s, 9H); ⁵¹V NMR (CD₃OD, 132 MHz) δ −565.0; ¹³C NMR(CD₃OD, 126 MHz) δ 180.1, 168.9, 161.7, 143.5, 138.6, 132.4, 129.5,129.4, 121.9, 84.7, 49.6, 49.3, 49.2, 49.0, 48.8, 48.6, 48.4, 38.3,36.3, 35.3, 31.8, 30.3, 28.1; IR (KBr) 3370 (br, w), 2959 (w), 2871 (w),1698 (m), 1668 (m), 1620 (s, C═N), 1580 (w), 1524 (m, COO), 1480 (w),1456 (w), 1373 (w), 1322 (w), 1285 (w), 1182 (w), 1071 (w), 986 (m,V═O); [α]_(D) ³⁴ +36.53 (c 0.1, CH₂Cl₂); TLC R_(f) 0.37 (CH₃OH/CH₂Cl₂,1/8); HRMS (ESI) [M+H]⁺ Calcd for C₂₂H₃₄NO₅V: 444.1959, found: 444.1949.

Catalyst (II-2)

Yield: 57%; black solid. ¹H NMR (CD₃OD, 400 MHz) δ 8.54 (bs, 1H), 7.66(d, J=2.4 Hz, 1H), 7.62 (d, J=2.4 Hz, 1H), 4.15 (s, 1H), 3.33 (s, OCH₃),1.44 (s, 9H), 1.18 (s, 9H); ⁵¹V NMR (CD₃OD, 105 MHz) δ −567.6; ¹³C NMR(CD₃OD, 126 MHz) δ 167.7, 142.3, 136.9, 136.2, 135.0, 134.6, 123.7,111.9, 84.7, 49.8, 38.3, 37.2, 36.2, 29.9, 28.0, 27.4; IR (KBr) 2965(s), 2913 (m), 2869 (m), 1663 (s), 1615 (s, C═N), 1578 (m), 1548 (m,COO), 1480 (w), 1429 (m), 1368 (m), 1320 (m), 1297 (s), 1181 (m), 1055(w), 1031 (w), 993 (m, V═O); [α]_(D) ³⁴ −126.4 (c 0.1, CH₃OH); TLCR_(f)0.20 (CH₃OH/CH₂Cl₂, 1/9); HRMS (ESI) [M+H]⁺ Calcd for C₁₈H₂₅BrNO₅V:466.0427; found: 466.0428.

Catalyst (II-3)

Yield: 75%; black solid. ¹H NMR (CD₃OD, 400 MHz) δ 8.56 (bs, 1H), 7.96(d, J=2.3 Hz, 1H), 7.78 (d, J=2.3 Hz, 1H), 4.18 (s, 1H), 1.20 (s, 9H);⁵¹V NMR (CD₃OD, 105 MHz) δ −557.0; ¹³C NMR (CD₃OD, 126 MHz) δ 179.1,167.2, 159.6, 141.7, 136.7, 123.6, 114.8, 110.9, 84.8, 49.9, 38.2, 28.1,36.2, 29.9, 28.0, 27.4; IR (KBr) 3370 (br, w), 2959 (w), 2871 (w), 1698(m), 1668 (m), 1620 (s, C═N), 1580 (w), 1524 (m, COO), 1480 (w), 1456(w), 1373 (w), 1322 (w), 1285 (w), 1182 (w), 1071 (w), 986 (m, V═O);[α]_(D) ³⁴ −40.8 (c 0.1, CH₂Cl₂); TLC R_(f)0.12 (CH₃OH/CH₂Cl₂, 1/10);HRMS (ESI) [M+H]⁺ Calcd for C₁₄H₁₆Br₂NO₅V: 489.8880, found: 489.8888.

Catalyst (II-4)

Yield: 81%; black solid. ¹H NMR (CD₃OD, 400 MHz) δ 8.71 (bs, 1H), 8.54(d, J=2.6 Hz, 1H), 8.39 (d, J=2.5 Hz, 1H), 4.24 (s, 1H), 3.31 (s, OCH₃),1.49 (s, 9H), 1.22 (s, 9H); ⁵¹V NMR (CD₃OD, 105 MHz) δ 549.8,-568.8; ¹³CNMR (CD₃OD, 126 MHz) δ 168.0, 140.5, 139.1, 130.1, 130.0, 128.4, 127.6,121.5, 84.9, 38.3, 36.5, 29.7, 28.0; IR (KBr) 2965 (w), 2916 (w), 2879(w), 1627 (m, C═N), 1598 (m, COO), 1509 (w), 1326 (m), 1326 (w), 1225(w), 1187 (w), 1113 (w), 1034 (w), 990 (w), 927 (w, V═O); MS (ESI) 850(M₂O+H₂O, 90), 419 (MOH+H+, 9), 417 (MOH-1⁺, 100); [α]_(D) ³⁴ 83.93 (c0.1, CH₃OH); TLC R_(f) 0.30 (CH₃OH/CH₂Cl₂, 1/4); Anal. Calcd. For[(H₂O)MOH]: C, 46.80; H, 5.78; N, 6.42. Found: C, 45.57; H, 5.83; N,6.15.

Oxidative Cleavage

In a flame-dried, 50-mL, two-necked, round-bottomed flask was placed 5mol % VO(OTf)₂. 5H₂O (11.8 mg, 0.025 mmol, 0.05 equiv) and 6 mol %additive (21.5 mg, 0.030 mmol, 0.06 equiv) and trifluoromethyl- orperfluoromethyl-containing reagent (346.6 mg, 1.05 mmol, 1.5 equiv)dissolved in 2.5 mL acetone. Then, α-methylstyrene (65 μL, 0.70 mmol,1.0 equiv) was added. After having the reaction finished, the solventwas removed in vacuo, and the crude product was purified by using flashcolumn chromatography on silica gel (ethyl acetate/hexane=1/8) to affordthe product. The result is shown in Table 1.

TABLE 1 Trifluoromethyl- Time Yield Embodiment Catalyst containingreagent Additive (h) (%) A-1 Cu(CH₃CN)₄PF₆

36 28 A-2 VO(OTf)₂•5H₂O

48 56 A-3 VO(OTf)₂•5H₂O CF₃SO₂Na (1.2 eq)

96 80 A-4 II-1

— 48 81 A-5 II-2

— 48 86 A-6 II-3

— 46 97 A-7 II-4

— 46 82

It can be found in Table 1 that the yield is low (28%) when theoxidative cleavage was performed with commercial catalyst Cu(CH₃CN)₄PF₆.The yield can be doubled or tripled when the catalyst V(O)(OTf)₂ wasused in the reaction. When the reaction was performed with the catalystof Formula (II-1) to Formula (II-4), the yield (81-97%) is significantlyimproved.

In aflame-dried, 25-mL, two-necked, round-bottomed flask was placed 5mol % catalyst (eq II-3) and trifluoromethyl- orperfluoromethyl-containing reagent (1.5 equiv) dissolved in acetone (ImL). Then, a compound (1-1) (1.0 equiv) with an unsaturated double bondwas added. After having the reaction finished, the solvent was removedin vacuo, and the crude product was purified by using flash columnchromatography on silica gel (ethyl acetate/hexane=1/8) to afford theproduct. The result is shown in Table 2.

TABLE 2 Time Yield Embodiment R₁ R₂ (h) (%) B-1 C₆H₅ CH₃ 46 97 B-24-MeC₆H₄ CH₃ 46 96 B-3 4-PhC₆H₄ CH₃ 48 90 B-4 4-ClC₆H₄ CH₃ 47 95 B-54-BrC₆H₄ CH₃ 47 93 B-6 4-NO₂C₆H₄ CH₃ 144 96 B-7 4-CH₃CO₂C₆H₄ CH₃ 72 92B-8 4-MeOC₆H₄ CH₃ 84 95 B-9 3-MeC₆H₄ CH₃ 47 91 B-10 2-MeC₆H₄ CH₃ 46 93B-11 2-Naphthyl CH₃ 46 90 B-12 4-Py CH₃ 120 92 B-13 2-Py CH₃ 144 90 B-142-Th CH₃ 45 93 B-15 cyclohexyl CH₃ 50 92

With the catalyst of Formula (II-3) of the present disclosure, theoxidative cleavage is carried out without adding additives. Theresultant product with high isolated yield (90-97%) can be obtained inthe aromatic system, and the reaction time is 46 to 144 hours. Also, theresultant product with high isolated yield (90-93%) can be obtained inthe heteroaryl system, and the reaction time is 45 to 144 hours. Theisolated yield is up to 92% in the cycloalkyl system, and the reactiontime is 50 hours.

In addition, through ¹⁹F NMR spectroscopic analysis, it is found thatthe other half of the main oxidative cleavage is converted totrifluoromethylketone or trifluoroaldehyde and trifluoroethanol (or thecorresponding trifluoromethyl alcohol) rather than formaldehyde or1,3,5-trioxane after the oxidative cleavage.

The reaction was performed in the same manner as described above, andthe result is shown in Table 3.

TABLE 3 Yield Embodiment R₁ R₂ Time (h) (%) C-1 C₆H₅ CH₂Br 193 91 C-2C₆H₅ Cy-Pr 90 89 C-3 C₆H₅ Cy-hex 96 95 C-4 C₆H₅ t-Bu 192 92 C-5 C₆H₅ Ph48 95 C-6

45 95

It was found that if R₁ of the compound (I) with an unsaturated doublebond was designated as phenyl to perform the oxidative cleavagereaction, the isolated yield was 91-92% with a longer reaction time(192-193 hours) when R₂ was an alkyl system. When R₂ was a cycloalkylsystem, the yield is 89-95%, and the reaction time was shortened to90-96 hours. In addition, when R₂ is aryl or R₁ and R₂ are fused to bean aralkyl system, the yield is up to 95%, and the reaction time issignificantly reduced to 45-48 hours.

The reaction was performed in the same manner as described above, andthe result is shown in Table 4.

TABLE 4 Time Yield Embodiment R₁ R₃ (h) (%) D-1 H CH₃ 96 60  D-2 CH₃ CH₃96 82^(a) ^(a)the reaction was performed at 50° C.

The reaction was performed in the same manner as described above, andthe result is shown in Table 5.

TABLE 5 Time Yield Embodiment Ar (h) (%) E-1 4-XC₆H₄ ^(b) 17-24 38-40E-2 4-CH₃CO₂C₆H₄ 26 41 E-3 4-Me or 4-PhC₆H₄ 18-19 41-43 E-4 3-ClC₆H₄ 9662 E-5 2-XC₆H₄ ^(b) 20-26 58-65 ^(b)X is halogen (F, Cl, Br, I)

When the R₂ and R₃ of the compound (I) with an unsaturated double bondis H, the corresponding benzaldehyde, trifluoroaldehyde andtrifluoroethanol can be obtained.

¹H NMR (CDCl₃, 400 MHz) δ 7.97-7.95 (m, 2H), 7.58-7.54 (m, 1H),7.84-7.44 (m, 2H), 2.6 (s, 3H); ¹³C NMR (CDCl₃, 125 MHz) δ 198.0, 137.0,133.0, 128.4, 128.2, 26.4; TLC R_(f) 0.32 (EtOAc/Hexane=1/15); HRMS (FI)Calcd for C₈H₈O: 120.0570, found: 120.0569.

¹H NMR (CDCl₃, 400 MHz) δ 7.86-7.85 (m, 2H), 7.26 (d, J=7.6 Hz, 2H),2.58 (s, 3H), 2.41 (s, 3H); ¹³C NMR (CDCl₃, 125 MHz) δ 197.8, 143.9,134.7, 129.2, 128.4, 26.5, 21.60; TLC R_(f) 0.25 (EtOAc/Hexane=1/15);HRMS (FI) Calcd for C₉H₁₀O: 134.0726, found: 134.0725.

¹H NMR (CDCl₃, 400 MHz) δ 8.05-8.02 (m, 2H), 7.71-7.68 (m, 2H),7.65-7.62 (m, 2H), 7.50-7.45 (m, 2H), 7.43-7.38 (m, 2H), 2.65 (s, 3H);¹³C NMR (CDCl₃, 125 MHz) δ197.7, 145.8, 139.9, 135.9, 128.9, 128.9,128.2, 127.3, 127.2, 26.6; TLC R_(f)0.3 (EtOAc/Hexane=1/10); HRMS (FI)Calcd for C₁₄H₁₂O: 196.0883, found: 196.0822.

¹H NMR (CDCl₃, 400 MHz) δ 7.91-7.87 (m, 2H), 7.45-7.41 (m, 2H), 2.59 (s,3H); ¹³C NMR (CDCl₃, 125 MHz) δ 196.7, 139.5, 135.4, 129.6, 128.8, 26.4;TLC R_(f) 0.23 (EtOAc/Hexane=1/20); HRMS (FI) Calcd for C₈H₇ClO:154.0180, found: 154.0181.

¹H NMR (CDCl₃, 400 MHz) δ 7.84-7.81 (m, 2H), 7.62-7.60 (m, 2H), 2.59 (s,3H); ¹³C NMR (CDCl₃, 125 MHz) δ 196.9, 135.8, 131.9, 129.8, 128.3, 26.5;TLC R_(f) 0.28 (EtOAc/Hexane=1/15); HRMS (FI) Calcd for C₈H₇BrO:197.9675, found: 197.9676.

¹H NMR (CDCl₃, 400 MHz) δ 8.33-8.29 (m, 2H), 8.12-8.09 (m, 2H), 2.68 (s,3H); ¹³C NMR (CDCl₃, 125 MHz) δ 196.2, 150.4, 141.4, 129.3, 123.8, 26.9;TLC R_(f) 0.35 (EtOAc/Hexane=1/5); HRMS (FI) Calcd for C₈H₇NO₃:165.0420, found: 165.0421.

¹H NMR (CDCl₃, 400 MHz) δ 8.00-7.97 (m, 2H), 7.20-7.16 (m, 2H), 2.58 (s,3H), 2.31 (s, 3H); ¹³C NMR (CDCl₃, 125 MHz) δ 196.8, 168.8, 154.3,134.7, 129.9, 121.7, 26.5, 21.1; TLC R_(f)0.30 (EtOAc/Hexane=1/5); HRMS(FI) Calcd for C₁₀H₁₀O₃: 178.0624, found: 178.0625.

¹H NMR (CDCl₃, 400 MHz) δ 7.95-7.92 (m, 2H), 6.95-6.91 (m, 2H), 3.87 (s,3H), 2.55 (s, 3H); ¹³C NMR (CDCl₃, 125 MHz) δ 196.7, 163.5, 130.6,130.4, 113.7, 55.4, 26.3; TLC R_(f) 0.35 (EtOAc/Hexane=1/5); HRMS (FI)Calcd for C₉H₁₀O₂: 150.0675, found: 105.0676.

¹H NMR (CDCl₃, 400 MHz) δ 7.77-7.37 (m, 2H), 7.39-7.26 (m, 2H), 2.59 (s,3H), 2.41 (s, 3H); ¹³C NMR (CDCl₃, 125 MHz) δ 198.3, 138.3, 137.1,133.8, 128.7, 128.4, 125.5, 26.5, 21.2; TLC R_(f)0.21(EtOAc/Hexane=1/20); HRMS (FI) Calcd for C₉H₁₀O: 134.0726, found:134.0724.

¹H NMR (CDCl₃, 400 MHz) δ 7.71-7.68 (m, 1H), 7.40-7.36 (m, 1H),7.29-7.24 (m, 2H), 2.58 (s, 3H), 2.53 (s, 3H); ¹³C NMR (CDCl₃, 125 MHz)δ 201.7, 138.3, 137.6, 132.0, 131.4, 129.3, 125.6, 29.5, 21.5; TLC R_(f)0.25 (EtOAc/Hexane=1/20); HRMS (FI) Calcd for C₉H₁₀O: 134.0726, found:134.0724.

¹H NMR (400 MHz, CDCl₃) δ 8.48 (s, 1H), 8.04 (dd, J=8.6, 1.4 Hz, 1H),7.97 (d, J=8.0 Hz, 1H), 7.91-7.87 (m, 2H), 7.63-7.54 (m, 2H), 2.74 (s,3H); ¹³C NMR (125 MHz, CDCl₃) δ 198.1, 135.6, 134.5, 132.5, 130.2,129.5, 128.4, 128.4, 127.8, 126.7, 123.9, 26.7; TLC R_(f) 0.20(EtOAc/Hexane=1/20); HRMS (FI) Calcd for C₂H₁₀O: 170.0726; found:170.0721.

¹H NMR (CDCl₃, 400 MHz) δ 8.80 (dd, J=4.4, 1.6 Hz, 2H), 7.72 (dd, J=4.4,1.6 Hz, 2H), 2.62 (s, 1H); ¹³C NMR (CDCl₃, 100 MHz) δ 196.6, 150.2,142.0, 120.5, 25.9; TLC R_(f) 0.20 (EtOAc/Hexane=1/3); HRMS (FI) Calcdfor C₇H₇NO: 121.0522, found: 121.0522.

¹H NMR (CDCl₃, 400 MHz) δ8.68 (td, J=4.0, 0.8 Hz, 1H), 8.03 (dd, J=8.0,0.8 Hz, 1H), 7.82 (dt, J=7.8, 1.6 Hz, 1H), 7.44-7.48 (m, 1H), 2.72 (s,3H); ¹³C NMR (CDCl₃, 100 MHz) δ 199.4, 153.1, 148.6, 136.4, 136.1,126.7, 121.1, 25.3; TLC R_(f) 0.25 (EtOAc/Hexane=1/5); HRMS (FI) Calcdfor C₇H₇NO: 121.0522, found: 121.0521.

¹H NMR (400 MHz, CDCl₃) δ 7.70 (dd, J=3.5, 1.2 Hz, 2H), 7.64 (dd, J=4.9,1.2 Hz, 1H), 7.13 (dd, J=4.9, 3.5 Hz, 2H), 2.57 (s, 3H); ¹³C NMR (125MHz, CDCl₃) δ 190.6, 144.5, 133.7, 132.4, 128.0, 26.8; TLC R_(f) 0.30(EtOAc/Hexane=1/10); HRMS (FI) Calcd for C₆HOS: 126.0134, found:126.0133.

¹H NMR (CDCl₃, 400 MHz) δ 2.34-2.30 (m, 1H), 2.11 (s, 3H), 2.19-1.84 (m,2H), 1.79-1.74 (m, 2H), 1.67-1.63 (m, 1H), 1.33-1.19 (m, 5H); ¹³C NMR(CDCl₃, 100 MHz) δ 212.3, 51.4, 28.4, 27.8, 25.8, 25.6; TLC R_(f) 0.21(EtOAc/Hexane=1/15); HRMS (FI) Calcd for C₈H₁₄O: 126.1039, found:126.1036.

¹H NMR (CDCl₃, 400 MHz) δ 8.00-7.98 (m, 2H), 7.64-7.60 (m, 1H),7.52-7.50 (m, 2H), 4.46 (s, 2H); ¹³C NMR (CDCl₃, 125 MHz) δ 191.3,134.0, 134.0, 128.9, 128.8, 30.9; TLC R_(f) 0.25 (EtOAc/Hexane=1/20);HRMS (EI) Calcd for C₈H₇BrO: 197.9675, found: 197.9679.

¹H NMR (CDCl₃, 400 MHz) δ 8.03-8.00 (m, 2H), 7.59-7.54 (m, 1H),7.50-7.45 (m, 2H), 2.71-2.65 (m, 2H), 1.27-1.23 (m, 2H), 1.07-1.02 (m,2H); ¹³C NMR (CDCl₃, 125 MHz) δ 200.5, 137.9, 132.6, 128.44, 127.9,17.0, 11.5; TLC R_(f) 0.20 (EtOAc/Hexane=1/15); HRMS (FI) Calcd forC₁₀H₁₀O: 146.0726, found: 146.0727.

¹H NMR (CDCl₃, 400 MHz) δ 7.94 (d, J=7.2 Hz, 2H), 7.55 (tt, J=7.2, 2.0Hz, 1H), 7.46 (t, J=7.4 Hz, 2H), 3.26 (tt, J=11.2, 3.2 Hz, 1H),1.91-1.82 (m, 4H), 1.76-1.72 (m, 1H), 1.55-1.25 (m, 5H); ¹³C NMR (CDCl₃,100 MHz) δ 203.9, 136.4, 132.7, 128.6, 128.3, 45.6, 29.4, 26.0, 25.9;TLC R_(f) 0.3 (EtOAc/Hexane=1/10); HRMS (FI) Calcd for C₁₃H₁₆OF₃:188.1196, found: 188.1195.

¹H NMR (CDCl₃, 400 MHz) δ 7.70-7.67 (m, 2H), 7.47-7.37 (m, 3H), 1.35 (s,9H); ¹³C NMR (CDCl₃, 125 MHz) δ 209.3, 138.6, 130.7, 128.0, 127.8, 44.2,28.0; TLC R_(f) 0.4 (EtOAc/Hexane=1/20); HRMS (FI) Calcd for C₁₁H₁₄O:162.1039, found: 162.1038.

¹H NMR (CDCl₃, 400 MHz) δ 7.82-7.80 (m, 4H), 7.62-7.57 (m, 2H),7.51-7.47 (m, 4H); ¹³C NMR (CDCl₃, 125 MHz) δ 196.7, 137.5, 132.4,123.0, 128.2; TLC R_(f)0.35 (EtOAc/Hexane=1/10); HRMS (FI) Calcd forC₁₃H₁₀O: 182.0726, found: 182.0725.

¹H NMR (CDCl₃, 400 MHz) δ 7.76 (d, J=7.2 Hz, 1H), 7.61-7.57 (m, 1H),7.50-7.47 (m, 1H), 7.39-7.35 (m, 1H), 3.15 (t, J=6.0 Hz, 2H), 2.71-2.68(m, 2H); ¹³C NMR (CDCl₃, 125 MHz) δ 206.9, 155.1, 137.0, 134.5, 127.2,126.6, 123.6, 36.1, 25.7; TLC R_(f)0.3 (EtOAc/Hexane=1/10); HRMS (FI)Calcd for C₉H₈O: 132.0570, found: 132.0570.

CF₃CH₂OH (Trifluoroethanol): ¹H NMR (400 MHz, CDCl₃) δ 3.92 (q, J=8.8Hz, 2H), 3.21 (br, 1H, OH); ¹⁹F NMR (470 MHz, CDCl₃) δ −79.08 (s).

CF₃CHO (Trifluoroacetaldehyde; b.p.−18° C.): ¹⁹F NMR (470 MHz, CDCl₃) δ−84.62 (s)

¹H NMR (CDCl₃, 500 MHz) δ 3.98 (sept, J=6.5 Hz, 1H), 3.17 (s, 1H, OH),1.38 (d, J=6.5 Hz, 3H); ¹⁹F NMR (470 MHz, CDCl₃) δ −81.4 (s).

¹H NMR (CDCl₃, 500 MHz) δ 2.48 (s, 3H); ¹⁹F NMR (470 MHz, CDCl₃) δ −80.0(s).

Although the present invention has been explained in relation to itspreferred embodiment, it is to be understood that many other possiblemodifications and variations can be made without departing from thespirit and scope of the invention as hereinafter claimed.

What is claimed is:
 1. A method for oxidative cleavage of a compoundwith an unsaturated double bond, comprising the steps of: (A) providinga compound (I) with an unsaturated double bond, atrifluoromethyl-containing reagent, and a catalyst;

wherein, R₁ and R₂ are each independently H, C₁₋₂₀ alkyl, C₃₋₂₀cycloalkyl, C₆₋₁₈ aryl, or C₄₋₁₈ heteroaryl, or R₁ and R₂ are fused tobe C₆₋₁₈ aralkyl; R₃ is H, C₁₋₁₀ alkyl, C₃₋₁₀ cycloalkyl, C₆₋₁₀ aryl, orC₄₋₁₀ heteroaryl, with the proviso that R₁, R₂ and R₃ are not H at thesame time; wherein the catalyst is represented by Formula (II):M(O)_(m)L¹ _(y)L² _(z)  (II) wherein, M is a metal selected from thegroup consisting of IVB, VB, VIB, and actinides; L¹ and L² are each aligand; m and y are integers greater than or equal to 1; and z is aninteger greater than or equal to 0; (B) mixing the compound with anunsaturated double bond and the trifluoromethyl-containing reagent toperform an oxidative cleavage of the compound with the unsaturateddouble bond by using the catalyst in air or under oxygen atmospherecondition to obtain a compound represented by Formula (III):


2. The method of claim 1, wherein R₁ and R₂ are each independently H,C₁₋₁₀ alkyl, C₃₋₁₀ cycloalkyl, C₃₋₁₄ aryl, or C₄₋₁₀ heteroaryl, or R₁and R₂ are fused to be C₆₋₁₂ aralkyl; R₃ is H, C₁₋₆ alkyl, C₃₋₆cycloalkyl, C₆₋₁₀ aryl, or C₄₋₁₀ heteroaryl.
 3. The method of claim 1,wherein L¹ is selected from the group consisting of OTf, OTs, NTf₂,halogen, RC(O)CH₂C(O)R, OAc, OC(O)R, OC(O)CF₃, OMe, OEt, O-iPr, andbutyl, wherein R is alkyl.
 4. The method of claim 1, wherein L² isselected from the group consisting of Cl, H₂O, CH₃OH, EtOH, THF, CH₃CN,

and ligand containing C═N unit.
 5. The method of claim 4, wherein theligand containing C═N unit comprises pyridine, oxazole, oxazoline, orimidazole.
 6. The method of claim 4, wherein the ligand containing C═Nunit is represented by Formula (IV):

wherein, R₄ and R₅ are each independently halogen, nitro, C₁₋₁₀ alkyl,C₆₋₁₈ aryl, or C₄₋₁₈ heteroaryl.
 7. The method of claim 5, wherein theligand containing C═N unit is represented by Formula (V):

wherein R₆ and R₇ are each independently H, C₁₋₅ alkyl or C₃₋₆cycloalkyl.
 8. The method of claim 1, wherein the catalyst representedby Formula (II) is MoO₂Cl₂, V(O)Cl₃, V(O)(O-iPr)₃, V(O)Cl₂, V(O)(OAc)₂,V(O)(O₂CCF₃)₂, Ti(O)(acac)₂, Zr(O)Cl₂, Hf(O)Cl₂, Nb(O)Cl₂, MoO₂(acac)₂,V(O)(OTs)₂, VO(OTf)₂, or V(O)(NTf₂)₂.
 9. The method of claim 1, whereinthe catalyst represented by Formula (II) is any one of formulas (II-1)to (II-4):


10. The method of claim 1, wherein the trifluoromethyl-containingreagent is 3,3-Dimethyl-1-(trifluoromethyl)-1,2-benziodoxole,3,3-Dimethyl-1-(perfluroalkyl)-1,2-benziodoxole,3-oxo-1-(trifluoromethyl)-1,2-benziodoxole,3-oxo-1-(perfluroalkyl)-1,2-benziodoxole), trifluomethyldibenzothiophenium salts, perfluoroalkyl dibenzothiophenium salts,CF₃SO₂Na, or CF₃(CF₂)_(n)SO₂Na, wherein n is an integer of 1 to
 6. 11.The method of claim 1, wherein step (B) further obtains atrifluoroketone- or trifluoroaldehyde-containing compound,trifluoroalkyl alcohol or a combination thereof:

wherein R₃ is H, C₁₋₁₀ alkyl, C₃₋₁₀ cycloalkyl, C₆₋₁₀ aryl, or C₄₋₁₀heteroaryl; n is an integer of 0 or 1 to 6.